Urea pyridinium compounds



Patented a. 16, 1945 7 UNITED STATES PATENT OFFICE UREA PYRIDINIUM COMPOUNDS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo.,

assignors to Petrolite Corporation, Ltd., WilmingtomDeL, a

corporation of Delaware N 0 Drawing. Original application June 23, 1943, Serial No. 492,183, now Patent No. 2,372,257, dated March 27, 1945. Divided and this application April 7, 1944, Serial No. 530,045

7 Claims.

particularly adapted for use as a demulsifier inv the resolution of crude oil emulsions.

Another object of our invention is to provide a novel method for producing said new material or composition of matter.

Briefly described, our new chemical product consists of certain pyridinium compounds containing (a), a high molal monocarboxy acyl radical; and (b) an urea nucleus. The type of chemical compound herein contemplated, as far as its major aspect is concerned, may be obtained in the following manner: urea, or a substituted urea, and particularly a monoalkyl or dialkyl urea, is treated with an oxyalkylating agent, such as ethylene oxide, so as to introduce at least two hydroxyl radicals, preferably as separate oxyalkylene or polyoxyalkylene radicals. Such polyhydric urea derivative is then esterified with a high molal monocarboxy acid having at least 8 carbon atoms and not more than 32 carbon atoms. The high molal monocarboxy acids may be exemplified by the higher fatty acids. The esterification is conducted so that there is present at least one unesterified hydroxyl radical. Such esterified oxyalkylated urea or oxyalkylated substituted urea, is reacted withone or more moles of a pyridine hydrohalide, such as pyridine hydrochloride, or its equivalent, so as to obtain the new compound or composition of matter herein contemplated. The method of preparation and the structure ofthe compound will be described subsequently in greater detail. It is well known that certain pyridinium compounds are obtainable by reactions involving the elimination of a mole of water formed by reaction betweena pyridinium hydrogen atom and the hydroxyl of a hydroxy'ethyl group or the like. (For example, see U. S. Patent-No, 2,273,181,

I dated February 17, 1942, toDe Groote & Keiser;

and also U. S. Patent No. 2,290,417, dated July 21, 1942, to De Groote and Keiser.)

It is well known that certain monocarboxy organic acids containing 8 carbon atoms or more and not more than 32' carbon atoms, are characterized by the fact that they combine with alkalies to produce soap or soap-like materials. These convenience, these acids will be indicated by the formula R.COOH. Certain derivatives of detergent-forming acids react with alkali to produce soap or'soap-like materials, and are the obvious equivalent of the unchanged or unmodified detergent-forming acids; for instance, instead of fatty acids, one might employ the chlorinated fatty acids. employ the hydrogenated resin acids. naphthenic acids, one might employ brominated naphthenic acids, etc.

The fatty acids are of the type commonly referred to as higher fatty acids; and of course, this is also true in regard to derivatives of the kind indicated, insofar that such derivatives are obtained from higher fatty acids. The petroleum dation of wax, parafiin, etc. Such acids may have as many as 32 carbon atoms. For instance,

, see U. S. Patent No. 2,242,837, dated May 20,

detergent-forming acids include fatty acids, resin acids, petroleum acids, etc. For the sake of ated fatty acids having 18 carbon atoms. unsaturated fatty acids include the fatty acids,

1941, to Shields. r

We have found that by far the most effective demulsifying agents are obtained from unsatur Such such as oleic acid, ricinoleic acid, linoleic acid, linolenic acid, etc. One may employ mixed fatty acids, as, for example, the fatty acids obtained from hydrolysis of cottonseed oil, soyabean oil, corn oil, etc. When our new product is intended to be used as a demulsifler, it is preferably ob-" 23, 1940, to Hoefielmann. As typical examples of applicable compounds may be mentioned glycerine epichlorhydrin, glycidealcohol, ethylene oxide, propylene oxide, butene-Z-oxide, butene-l-oxide,

isobutylene oxide, butadiene oxide, butadiene di' oxide, chloroprene oxide, isoprene oxide, decene oxide, styrene oxide, cyclohexylene oxide, cyclopentene oxide, etc.

As to the reaction of ureas'or substitutedureas, followed 'by esterification with a high molal hydroxy acid, reference is made to U. S. Patent No. 2,083,221, dated June 8, 1931, to De Groote. (See also U. S. Patent No. 2,059,273, dated November 3, 1936, to Piggott.) It is to be noted that in light of present knowledge, there i considerable doubt that any free amino hydrogen atoms Instead of the resin acids, one might,

Instead of of a reactant containing a reactive ethylene oxide ring. Furthermore, it is to be noted that the aforementioned patents are concerned with materials which are essentially soluble, i. e., watersoluble esterified oxyalkylated ureas or substituted ureas. In the present instance such esters need not be water-soluble, and as a matter of fact,

. we prefer to use the particular type of reactant which is water-insoluble prior to reaction with pyridine hydrochloride, or its equivalent. In other words, it is our preference that the solubility be obtained at least largely, and preferably,.en-

tirely through the introduction of the pyridinium radical or radicals.

Members of the pyridine series suitable as reactants include pyridine, alkylated derivatives of pyridine, particularly alkylated derivatives in which the, alkyl radical contains three carbon atoms or less, and especially methylated pyridines,

i. e., pyridines in which one, two, or three methyl OxYALxYLArsn UREA DERIVATIVE Example 1 1 pound mole of urea is reacted with 4 pound moles of ethylene oxide at a temperature of approximately 100 C. for approximately 6 hours, with constant stirring, until all of the ethylene oxide is absorbed. The ethylene oxide need not be added at one time, but may be added intermittently. In such event, the period of reaction may be considerably longer. If desired, one-half of 1% of sodium methylate may be used as a catalyst.

OXYALKYLATED Um Dnarva'rrvs 4 Example 2 The same procedure is followed as in Exampl 1, preceding, except that the amount of ethylene oxide employed per mole of urea is doubled.

OXYALKYLATED Una Dnarvarrvr:

Example 3 f Thesame procedure is followed as in Example 1, preceding, except that the amount of ethylene oxide per mole is tripled.

Oxvsrxnsrsn Um Daiuvarrvs Example 4 Diamyl urea is prepared from amylene Cand a climate. (See Berichte, 12, 1331 Custer.) Such substituted urea is treated with ethylene oxide in Also suitable as reassess? 'remain in presence of treatment with an excess OXYALKYLATED Dznrvsrm Example 6 The same procedure is followed as in Example 4, preceding, except that the corresponding benzyl urea is substituted for diamyl urea.

OXYALKYLATED Um DERIVATIVE Example 7 5 I The same procedure is followed as in Example 4, preceding, except that the corresponding phenyl urea is substituted for diamyl urea.

Oxnnxmrsn UREA Dsarva'rrvs Example 8 N-mono-n-buty1 urea cinimrcomii is substituted for amyl urea in Example 4, preceding.

OXYALKYLATED Um Dsarva'rrvs Example 9 N,N' di-n-butyl urea (C'iHs) HNCONH C4H9 is substituted for amyl urea in Example 4, preceding.

Oxxsnxnarsn Um Dsarvarrvr:

Example 10 N,N-di-n-butyl urea (C4H9)2NCONH2 is substituted for amyl urea in Example 4, preceding.

Oxrarxnsrsn UREA Dsarvsrrvs Example 11 N-mono-n-butyl thiourea C HsNHCSNHz substituted for amyl urea in Example 4, preceding.

oxnrxrmrsn Uam DERIVATIVE Example'lz Other alkylene oxides, such as propylene oxide, butylene oxide, or glycidol, are substituted for ethylene oxide in Examples 1 to 11, preceding.

Esrnss or oxranxrLa-rsn ,Uass Drarvsrrvss Example 1 Oxyalkylated urea derivatives, as exemplified by Examples 1 to 12, preceding, are esterifledwith oleic acid in equimolar proportions, to give the desired ester. (See procedure described in aforementioned De Groote Patent No. 2,083,221.)

Esrras' or Oxnnmsrsn UREA Drarvarrvrs Example 2 Ricinoleic acid is substituted it: oleic acid in Example 1, preceding.

Esrsas or Oxxatxrmrrn Urns Driuva'rrvrs Example 3 Stearic acid is substituted for oleic acid in Example 1, preceding.

thesame manner as Examples 1, 2 and 3, preceding.

Oxnnxnarrn Um Dmuvirrrvs Example 5 The same procedure is followed asin the preceding example, except that the corresponding Esrms or Oxnnmsrnn Um Drsrvarrvss Example 4 Naphthenic acids derived from Gulf Coast crude petroleum are substituted for oleic acid in Example 1, preceding.

Esrzns or Oxxatmarso UREA Dsnrvs'rrvrs Example 5 Mixed fatty'acids derived from soyabean oil are substituted for oleic acid in Example 1, precyclohexyl urea is substituted for diamyl urea. cedin Esrrms or Oxxarmarnn Um Dmizvarrvns Example 6 Linseed oil fatty acids are substituted for oleic acid in Example 1, preceding.

Es'rms or Oxrnmarsn Uaaa Dmuvarrvss Example 7 In the preceding examples where there are present at least 3 hydroxyl radicals, and preferably, 4 hydroxyl radicals, 2 moles of the fatty acids are employed instead of a single mole.

PYRIDINIIJ'M Comoum) v 1 mole of urea is treated with 4.- moles of ethylene oxide to give tetraethanol urea ofv the following formula:

OH C:H4/ (hHiOH Such material is then esterifled with a mole of ricinoleic acid indicated by the formula'R.COOH,

to give the resultant ester of the following composition:

One pound mole of an ester of the kind describedv immediately preceding is mixed with one pound mole of a hydrochloride of afraction of pyridine bases (50% distilling, up to 140 0., 90% distilli up to 160 C. completely soluble in water), and

Emmple 5 The same procedure is followed as in Examples 1 to 4, preceding, except that the amount of ethylene oxide is employed is doubled.

Example 6 The same procedure is followed as in Examples 1 to 4, preceding, except .that the amount of ethylene oxide employed is tripled.

Example 7 The same procedure is followed as in Examples 1 to 6; preceding, except that propylene oxide,

butylene oxide, or glycide is substituted for ethylene oxide in Examples 1 to 6, preceding.

Example 8 The same procedure is followed as in Example 1, prece i g. exceptthat the esterification involves 2 moles of ricinoleic acid for each mole of tetrahydroxyethyl urea.

Example 9 The same procedure is employed as in Example 1, preceding, exceptthat the amount of pyridine hydrochloride per mole of tetrahydroxyethyl urea is doubled.

Example 10 Thesame procedure is followed in preceding Examples 1 to 9, inclusive, except that one substitutes instead the various esters of oxyalkylated urea derivatives exemplified by Example 1 to '7, preceding, 'to the extent that they are different 85 from the type already employed in Examples 1 to one-third pound mole of a mixture of free bases are heated at 100 C., or even higher, for onehalf to 5 hours.

Furthermore, at 150 to 160 C. the reactionis more rapid. T

Furthermore, pure pyridine may be employed instead of a mixture of the bases. (Compare with Example 2 of Haack Patent No. 2,242,211.)

.The excess of free pyridine maybe removed at the end of the reaction.

Without attempting to specify any specific isomer, but simply by way of illustration, the reaction employed may be indicated as follows:

C O H C aHa Example 2.

The oxyalkylated urea derived by treating one mole of N-mono-n-butyl urea C4HQHINCON'H2 with three moles of ethylene oxide is, reacted in the same manner as in Example 1, preceding.

Example 3 One pound mole of N,N'-di n-butyl urea (C4HQ)'HNCONH(C4H9) is treated with two pound moles of ethylene oxide and substituted as a reactant in the procedure outlined in Example 1, preceding.

Example 4 CIH(OOC.R

, One pound mole of N,N-di-n-butyl urea 9, preceding.

In light of what has been said, it is obvious that the invention may be considered in a somewhat broader aspect. For instance, urea might d0 be treated with two moles of ethylene oxide so as to yield a diethanol urea. Such a product would be perfectly satisfactory as a reactant. The

(C4119) zNCONHz is treated with 2 pound moles of ethylene oxide and substituted as a reactant in the procedure outlined in Example 1, preceding.

substituted ureas are not necessarily limited to the alkyl type, but as has been suggested previously, any hydrocarbon radical may serve as a substituent for an amino hydrogen atom. In other words, one or more of the amino hydrocarbon atoms, as indicated, may be replaced by an alkyl radical, anaryl radical, an aralkyl radical, or an alicyclic radical. In some instances,

such substituted ureas are available by reactions involving primary amines and diethyl carbonate, although unfortunately, the yields are extreme y low, even when conducted under pressure, or ev n.

when conducted in some other suitable manner.

It has been pointed out that the oxyalkylating agent includes glycide and the like. Hereinafter, and particularly in the claims, reference will be made to the alkylene oxides as alkylating agents, and more particularly,. in those instances where the number of'carbon atoms in the alkylene radical is less than ten, and preferably, not over four.

The other variants previously indicated are ob- .ion. Actually, any other suitable salt may apprinciple of metathesis.

nish the anion, reference is made to U. 8. Patent No. 2,295,167, dated September 8, 1942, to De Groote 8: Keiser. Briefly stated, the procedure employed is to neutralize pyridine or the equivalent with a selected sulfonic acid and then react the pyridine hydrosulfonate in the same manner as one would employ a pyridine iwdrohalide. Another procedure, of course, simply involves the The pyridinium chloride produced in the mannerpreviouslydescribed is reacted with the sodium sulfonate in an alcoholic solution, or, in some instances, in an aqueous solution. If the resultant compound, 1. e., a compound wherein the anion is the sulfonic acid radical, is water-insoluble, then precipitation takes place in aqueous solution. If, on the other hand, the resultant is water-soluble, then combination takes place in alcoholic solution by precipi-. tation of sodium chloride, which can be removed and the alcoholic solution distilled to eliminate the properties, i. e., some of the compounds may be water-wettable, some may be self-emulsiflable,

tract from clarity.

assess:

mula depicted is intended to include all the various isomeric forms and is not limited to the particular isomer shown. This is true insofar that isomers are all functional equivalents, and are, in fact, metamers. Any other treatment would result in a more involved claim, and perhaps de- Chemical products or compounds of the kind above described, are adapted to be used as demulsiflers in the resolution of petroleum emulsions of the water-in-oil' type; they are adapted to be used in the removal of a residual mud sheath which. remains'after drilling a well by acidification of calcareous oil-bearing strata by means of a strong mineral acid, such as hydrochloric acid; and some of said products are capable of use as wetting agents in the flooding of exhausted oil-bearing strata, and for various other uses where wetting agents of the conventional type are employed. As to some of such uses which are well known, see The Expanding Application of Wetting Agents, Chemical Industries, volume 48, page 324 (1941) Having thus described our invention, what we claim as new and desire to secure by Letters Pet some may produce cloudy solutions and others may produce clear soiutions.- Some'may show limited solubility in either oil or water.

In light of what has been said, the compounds 4 herein contemplated may be represented by the following formula, in conjunction with the ob- Yious equivalents previously referred to:'

- anion R: 0 (0.31.0) 0,111.1 5 Bi N i N I t m (c.m.o .".oon

in which RC0 is the acyl radical oi. a monocarboxy detergent-forming acid having at least 8 and not over 32 carbon atoms; RiiN represents a radical derived from a heterocyclic compound consisting of pyridine, quinoline, isoquinoline, and

' radical; m represents a small whole number not ent is: r

1. A new chemical product, comprising an urea pyridinium compound of the formula:

1 .5 alnicn in whichRCO is the acyl radical of a monocarboxy detergent-forming acid having at least 8 and 'not over 32 carbon atoms; mm is a heterocyclic radical selected from the class consisting of pyridine radicals, quinoline radicals, isoquinoline radicals, and C-methyl linked homologues thereof; R: and'Ra are members of the class consisting of hydrogen atoms hydrocarbon radicals greater than -10, 1i is a small whole number vary- 'ing from 2 to 10: and m. represents an integer varying from o to 10; R: and it: maybe the same ordiflerent. a is preferably 2, 3 or 4. it is obvious that the-above formula represents an isomer, whereas, variousoth'er isomeric i'orms may be obtained. Any particular'isomer may serve, or a'mixture of isomers. For the sakeofbrevity,

having less than 8 carbon atoms and selected from the class consisting of alwl radicals, aryl radicals, aralkyl radicals, alicyclic radicals, and

the radicals alnlon aHn LrC-Hr-NE R1 and I IH,IQ)I'- V i I in which m represents a small whole number not greater than 10, n represents a small whole number greater than one and not greater than 10 and m represents an integer varying from 0 to 10.

2. A new chemical product, comprising an urea p ridinium compound of the formula:

I alnlon B o (ca ln ICIHII E RI ni (cmaomoon' in whichRCOis the acyl radical ofa higher fatty acid having at least 8 and not over 32 carbon atoms;. R158 is a heterocyclic radical selected from the class consisting of pyridine radicals, quinoline radicals, isoq-ulnoline radicals, and

.Q- methyl linked homologuesthereot; Re and Rs inthcheretoappendedclaimstheparticulariorcarbon atomsandselected iromthe class consisting of allryl radicals, aryl radicals, aralkyl radicals, alicyclic radicals, and the radicals v anion (CnH$1|o)mCnH2nI IE R1 and (CnHIn)n'-OCR in which m represents a small whole number not greater than 10, n represents a small whole number greater than one and not greater than 10, and m represents an integer varying from 0 to 10.

3. A new chemical product, comprising an urea I pyridinium compound of the formula:

anion in which RC0 is the acyl radical of an unsaturated higher fatty acid having at least 8 and not over 32 carbon atoms; RiEN is a heterocyclic radin which RC0 is the acyl radical of an unsaturated higher fatty acid having 18 carbon atoms; RN is a heterocyclic radical selected from the class consisting of pyridine radicals, quinoline radicals, isoquinoline radicals, and C-methyl linked homologues thereof; Rzand R3 are members of the class consisting of hydrogen atoms,

hydrocarbon radicals having less than 8 carbon atoms and selected from the class consisting of alkyl radicals, aryl radicals, aralkyl radicals, alicyclic radicals, and the radicals anion R1 and (CnHinO)m'-OCR in. which m represents a small whole number not greater than 10, n is a small whole number varyical selected from the class consisting of pyridine radicals, quinoline radicals, isoquinoline radicals, and C-methyl linked homologues thereof; R2 and Rs are members of the class consisting'of hydrogen atoms, alkyl radicals, aryl radicals, aralkyl radicals, hydrocarbon radicals having less than 8 carbon atoms and selected from the class consisting of alicyclic radicals,

and the radicals v in which m represents a" small whole number not greater than 10; n represents a small whole number greater than one and not greater than 10, agd m represents an integer varying from 0 to 4. A new chemical product, comprising an urea pyridinium compound of the formula:

anion in which RC0 is the acyl radical of an unsaturated higher fatty acid having 18 carbon atoms;

RiEN is a heterocyclic radical selected fromthe class consisting of pyridine radicals, quinoline radicals, isoquinoline radicals, and C-methyl' linked homologues thereof: R2 and R3 are members of the class consisting of hydrogen atoms,

hydrocarbon radicals having less than 8 carbon atoms and selected from the class consisting of alb'l radicals, aryl radicals, aralkyl radicals, ali- .cyclic radicals, and the radicals anion (CIHIO) -C.H:.N E R1 and (cmaoiwoon in which m represents a small whole number not 4 greater than 10; n represents a small whole num-- ber greater than one and not greater than 10, argon represents an integer varying from 0 5. A new chemical product, comprising an urea I pyridinium compound of the formula:

ing from. 2 to 10, and m represents an integer varying from 0 to 10.

6. A new chemical product, comprising a monoquaternary urea pyridinium compound of, the formula:

in which m represents a small whole number not greater than 10, n is a small whole number varying from 2 to 10, and m represents an integer varying from 0 to l0.

-7. Injthemeth'od of manufacturing a ureapyridinium compound of the formula:

anion R2 0 (0 en in ICIHIIN E 1 N-C- Rs (C..H:-0) .nOCB

as described in claim 1, the steps of (a) hydroxyalkylation of urea involving a reactant having not'overlil" carbon atoms; (b) esterification of t the oxyalkylated urea with a monocarboxy detergent-forming acid having at least 8 and notnot over 32 carbon atoms; and (0) reaction of the aforementioned ester and a pyridinium salt in which the heterocyclic radical is selected from the class consisting of pyridine radicals, quincline radicals, isoquinoline radicals and C-methyl linked homologues thereof.

rmnvm DE enoo'm. BERNHARD Kmsna. 

